Phonon Spectra and Phase Transitions in van der Waals Ferroics MM$'$P$_2$X$_6$

TL;DR

This study investigates phonon behavior and phase transitions in CuInP$_2$S$_6$, revealing acoustic softening linked to flexoelectric coupling and inhomogeneous polarization near the ferrielectric transition.

Contribution

It provides new insights into phonon softening mechanisms and the role of flexoelectric coupling in van der Waals ferroics during phase transitions.

Findings

Pronounced acoustic phonon softening observed below 330 K.

Hypersound velocity increases below 312 K with polarization rise.

Thermal conductivity decreases near the ferrielectric transition.

Abstract

For CuInP$_2$S$_6$ layered ferrielectric crystal, that is most investigated among wide family of van der Waals ferroics MM$'$P$_2$X$_6$ (M - Cu, Ag; M$'$ - In, Bi, Cr, $\dots$; X - S, Se), by Brillouin spectroscopy the temperature dependence of the longitudinal hypersound velocity was investigated for the acoustic phonons propagated in the plane of crystal layers. Pronounced softening of acoustic phonon branch is observed in the paraelectric phase below $T^{*} \approx 330~$K at cooling to temperature $T_C \approx 312~$K of the first order phase transition into ferrielectric phase. Below $T_C$ the hypersound velocity growth in correlation with spontaneous polarization rise and its temperature anomaly is similar to earlier observed temperature behavior of longitudinal ultrasound velocity for acoustic wave propagated normally to the structural layers. Determined anomalous part of the CuInP$_2$S$_6$ crystal thermal conductivity in the vicinity of ferrielectric transition also demonstrate lowering of the heat transferring phonons group velocity with cooling from $T^{*}$ to $T_C$. Observed acoustic softening obviously is induced by flexoelectric coupling of relaxational soft polar optic and acoustic branches that is related to inhomogeneously polarized state appearing between paraelectric and ferrielectric phases.